Bluish sulphurized indophenol dyes and process of making the same



. ture and in presence of benzidine.

Fatented Dec. 18, 1928.

'UNIT'EDHSTATES PATENT OFFICE.

HERMANN Bows AND ANDRE GATINEAU, or BASED, SWITZERLAND, Assrenons To THE FiRM SOCIETY or CHEMICAL INDUSTRY IN BASLE, or BASELSWITZERLAND.

' ZBLUISH ,SULPHUQRIZED INDOPHENOL DYES Ann rnoonss or MAKING THEsAME.

No Drawing. Application filed. November 9, 1925, Seria1 No. 68,024, and in Switzerland November 28, 1924.

In the United States Patent No. 1,565,736,

there have been described new bluishsuL phurized indophenol-benzidine dyes and process of making the same, obtained by .reducing the indophenols made from nitrosophenols and carbazole and treating the leucocompound with sulphur atraised tempera- These dyestuffs show higher capacity of dyeing and better properties of fastness than those made under the same conditions but without addition of benzidine.

It has now been found that by replacing the benzidine by aromaticv aminocompounds corresponding to hydrocarbons having less than 12 carbon atoms, such as aniline, the toluidines, the chloroanilines, the naphthylamines or the derivatives or parent materials of same, as for instance acetoanilide, carbanilide, diarylanilines, N alkylanilines, naphthylamines, nitroanilines etc., and by sulphurizing at raised temperature if desired in presence of a water soluble substratum such as common salt, sodium sul- I phate, sodium thiosulphate,ialkali metal carbonates, naphthalenetrisulphonate of sodium etc, also new, valuable, strong and fast vat dyestuffs are obtained. r

The new dyestuffs form dark powders insoluble in water, soluble in concentrated sulphuric acid with blue coloration, producing wit-h sodium hydrosulphite and caustic soda yellow vats and with alkali metal sulphides greenish vats which dye the vegetable fibre in blue to greenish-blue shades very fast to washing, to light and chlorine.

Example 1.

27.2 parts of the indophenol made by con densing nitrosophenol and carbazole are introduced into a concentrated solution of polysulphides from 29 parts of crystallized sodium sulphide and 10 parts of sulphur, the whole being stirred until the indophenol is completely reduced. The mass is then-dried. and carefully mixed with 16 parts of diphenylurea, 10 parts of sulphur and 10 parts of common salt. The mixture thus obtained is heated slowly to 180? with reduced or raised pressure, preferably with exclusion of oxygen, and kept for some hours at this tem perature. The productthus obtained is finely ground after cooling, washed, first with dilute sodium sulphide, then with Water, and finally with dilute hydrochloric acid in order stuff is obtained.

- ample by other amines.

to eliminate remaining aniline or organic bases; There is thus-obtained with excellent yield an intense bluedyeing dyestuif.

.By replacing in this example thediphenylurea by the o-ditol lurea a very similar dyeuch redder dyestuffs are obtained by replacing the ureas mentioned by the acetoanilide or the aceto-orthotoluidide.v Fast dyestuffs are also obtained if the indophenol is sulphurized in presence of p-toluene sulphanilide.

Example 2. 27 .2, parts of the indophenol made by condensing nitrosophenol and carbazole are-introducedinto a concentrated solution of polyapparatus, and the reaction product Worked up as usual. Y

The aniline may be re laced in this exaluable dyestuffs are obtained, among others, with the fol lowing bases: the orthoand paratoluidines,

dimethylaniline, the paranit-raniline, the. acetyl-paraparaphenylenediamine, the phenylenediamine and the diphenylamine. The dyestuffs obtained by means of the paratoluidine, the diphenylamine and the paranitraniline or the paraphenylenediamine are I distinguished by their greenish shade.

What We claim is:

1. The herein described process for the production of bluish sulphurized indophenol dyes by reducing the indophenols made from nitrosophenols and carbazole and sulphurizing the leucoderivat-ive thus obtained in pres ence of aromatic aminoco-mpounds corresponding to hydrocarbons having less than 12 carbon atoms at substantiallylSO".

2. The herein described process for the production of bluish sulphurized indophenol dyes by reducing the indophenols madejfrom nitrosophenols and carbazole and sulphurizence of, aromatic aminocompounds corre- 12 carbon atoms and of a water soluble substratum at substantially 180.

a I u 1 I 111g the leucoderivative thus obtained 1n presspondingto hydrocarbons having less than I 3. The herein described process for the production of bluish sulphurized indophenol dyes by reducing the indophenols made from nitrosophenols and carbazole and sulphurizing the leucoderivative thus obtained in presence of aromatic aininocoinpounds corr spending to hydrocarbons of the benzene series at substantially 180.

l. The herein described process for the production ofbluish sulphurized indophenol dyes by reducing the indophenols made from nitrosophenols and'carbazole and sulphur-i2- ing the leucoderivative thus obtainedin presence of aromatic aminocompounds correspending to hydrocarbons of the benzene se ries and of a- Water soluble substratum at substantially 180.

' 5 The herein described process for the production of bluish sulphurized indophenol dyes by reducing the indophenols made from nitrosophenols and carba-zol'e and sulphurizing the leucoderivative thus obtained in pres ence of aromatic ai'i'iinocon'ipounds corresponding to b'en zeneat substantially 180.

6: The herein described process for the production of bluish sulphurized indop'he-nol c yes by reducing the indop'henols made from nitrosophenols and earbazole andsulphuriw ing the leucoderivative thus obtained in presence of aromatic aininocoinpounds corresponding to benzene, and of common salt at substantially 180.

7. The herein described new bluish sulphurized indophenol dyestufis obtained by reducing the indophenolsniade from n1tro= sophenols and carbazole and sulphurizing at substantially 180 the detlCQClfl'lViitlVES thus obtained in presence of aromatic aininoconi- 8. Material dyed with the products of claim 7.

In Witness whereof We have hereunto 'BOTS. ANDRE CATINEAU.

si; ied our names this 29th dayof October, 

